ABSTRACT
Identifying the origin of scattering from polymer materials is crucial to infer structural features that can relate to functional properties. Here, we use our recently developed virtual-site coarse graining to accelerate atomistic simulations and show how various molecular features govern wide-angle X-ray scattering from a conjugated polymer, poly(3-hexylthiophene) (P3HT). The efficient molecular dynamics simulations can represent the structure and capture the emergence of crystalline order from amorphous melts upon cooling while retaining atomistic details of chain configurations. The scattering extracted from simulations shows good agreement with wide-angle X-ray scattering experiments. Amorphous P3HT exhibits broad scattering peaks: a high-q peak from interchain side-group correlations and a low-q peak from interchain backbone-backbone correlations. During amorphous to crystalline phase transitions, the distance between backbones along the side-group direction increases because of lack of interdigitation in the crystalline phase. Scattering from π-π stacking emerges only after crystallization takes place. Intrachain correlations contribute negligibly to the scattering from the amorphous and crystalline phases.
ABSTRACT
The local structure of conjugated polymers governs key optoelectronic properties, such as charge conduction and photogeneration at donor-acceptor interfaces. Because conjugated polymers are large, stiff, and relax slowly, all-atom molecular dynamics simulations are computationally expensive. Here, we describe a coarse-graining method that exploits the stiffness of constituent aromatic moieties by representing each moiety as rigidly bonded clusters of atoms wherein virtual sites replace several atoms. This approach significantly reduces the degrees of freedom while faithfully representing the shape and interactions of the moieties, resulting in 10 times faster simulations than all-atom simulations. Simulation of a donor polymer (P3HT) and a non-fullerene acceptor (O-IDTBR) validates the coarse-graining method by comparing structural properties from experiments, such as the density and persistence length. The fast simulation produces equilibrated systems with realistic morphologies. The simulation results of an equimolar mixture of P3HT, with a molecular weight of 1332 g mol-1, and an O-IDTBR mixture suggest that the interface width must be larger than 7 nm. Also, we investigate the effect of slow cooling on morphologies, particularly the number of close contacts that facilitates carrier transport. Slow cooling increases close contacts, and the effect is more pronounced in crystal-forming P3HT than in O-IDTBR, where bulky side-groups hinder crystal formation.
